Reduction of organic compounds



Patented June 13, 1944 REDUCTION OF ORGANIC COMPOUNDS Arthur L. Fox, Woodstown, N. J., assignor to E. I.

du Pont de Nemours 8: Company, Wilmington, Del., a corporation of Delaware No Drawing. Application March 25, 1942,

Serial No. 436,205

i 8 Claims. (01. 260-609) {This invention relates to the production of mixtures of aliphatic mercaptans. More particularly, it relates to the production of mixtures of saturated aliphatic mercaptans from mixtures of saturated aliphatic sulfonylhalides. Still more particularly, it relates to th production of mixtures of saturated aliphatic mereaptans of at least and-preferably at least 8 carbon atoms from mixtures of saturated aliphatic sulfonyl chlorides of the same. number of carbon atoms. The invention also relates to mixtures of novel mercaptans obtainable by such processes.

In one of its aspects the invention pertains to the production of mixtures of saturated aliphatic mercaptans containing a plurality of mercapto groups in the molecule from mixtures of saturated aliphatic polysulfonyl chlorides of at least 8 carbon atoms and to the products produced thereby.

In another aspect the invention is concerned with the production of mixtures of such aliphatic mercaptans containing chloro aliphatic mercaptans from mixtures of saturated aliphatic hydrocarbon and chlorohydrocarbon monoand polysulfonyl chlorides and mixtures of such sulfonyl chlorides containing at least 8 carbon atoms and to the mixtures of novel mercaptans obtainable thereby.

It is an object of this invention to produce new and useful mixtures of mercaptans. object is to produce mercaptans from hydrocarbon sulfonyl chloride derivatives. A more speciflc object of this invention is to produce mixtures of higher aliphatic mercaptans by reducing them. in the liquid phase with a strong reducing The above objects of the invention may be accomplished by the following invention which comprises reducing a mixture of homologous saturated aliphatic sulfonyl chloride derivatives with a strong reducing agent until at least a recoverable amount of mercaptan derivatives is f'formed. The mercaptan's can then be recovered and utilized and the remaining sulfonyl chlorides further reduced with the addition of further sulfonyl chlorides and/or reducing agents. The reaction may, for instance, be al- N lowed to proceed until a substantial amount of the mixture of aliphatic mercaptans separates out. It may be recovered from the reaction mass A further and purified by various physical and/or chemical methods.

The reaction can be carried out in an aqueous logous mixtures of aliphatic sulfonyl chlorides of at least 5 carbon atoms can be dispersed in water at normal or moderate temperatures, admixed with an acid, e. g. hydrochloric, sulfuric, acetic, etc., and a finely divided heavy metal, and the reaction mass heated to a moderate temperature. Suitable finely divided metals include zinc, iron andtih.

A preferred method of carrying out the invention resides in the use of a non-aqueous medium. In this preferred aspect of the invention an inert solvent or diluent is used and the reduction eifected by means of hydrogen in the presence.

of a hydrogenation catalyst. The mixture of saturated aliphatic sulfonyl chlorides of at least 5 carbon atoms may be admixed with the solvent and catalyst and hydrogen passed in. Mechanical agitation to keep the catalyst uniformly distributedmay be availed of. When the reduction has been carried out to completion or to the desired extent the mercaptan derivatives can be separated out by-adding water, extraction, and/or decantation and further purified by the methods outlined above.

The latter reduction may be carried out in a pressure vessel at temperatures from 50 to 200 C. and more. It has the advantage that the absence of water insures against the hydrolysis of the sulfonyl chloride derivatives to sulfonic acids. Solvents such as benzene, toluene, xylene, carbon tetrachloride, benzine, pentane, hexane, etc. can be used as reaction media.

It has been found that the organic sulfonyl chloride mixtures obtained 'by reacting saturated aliphatic hydrocarbons of at least 8 carbon atoms'including mixtures of such hydrocarbons, such as petroleum fractions, paraflin waxes, etc. with admixed sulfur dioxide and chlorine under conditions conducive of the formation of organic sulfonyl chlorides, can be converted into useful mercaptans by the above procedures. The preparation of the initial materials is described in U. S. Reissue 20,968, and in 2,202,791. In general, a complex homologous mixture of primary and secondary hydrocarbon and chlorohydrocarbon monoand poly-sulfonyl chlorides predominating in secondary sulfonyl chlorides are formed by the processes described in said patents.

The proportions of such ingredients can be varied by varying the reactants and conditions.

The mercap an f m mi p minating in -was vacuum distilled and some water and some polysuli'onyl chloride derivatives and/or containsulfur dioxide was first removed. The material ing high percentages of chlorineatoms attached was fractionated according to the following t to a carbon are quite unique and constitute imble: portant aspects of the invention. r

The invention will be further illustrated but F in m P cm is not intended to be limited by the following J33 stint 53' m8 1%; 3? examples.

' Example Mm Pg; Pee:

Thirty-five parts of zinc dust, 87 parts of wa- 8-3 -3 tru ter and 38 parts of a homologous mixture of D 1 3118 5%? m cetane sulfonyl chlorides, containing and consist- E H30 .5 ing of cetane andchlorocetane, primary and sec- 77 L20 82 ondary monoand polysulfonyl chlorides, 23.65% I chlorine and 12.21% sulfur, prepared according m this table it is pp r t that this reduc- \to the teachings of U. s. patent, Reissue 20,968, will also removes a nsiderable portion or the while irradiating with light from a tungsten flla- Qhain halogen and leaves its P an satment light bulb, were admixed and heated on a rated mereeptenwater bath, the temperature rising to 80 C. be- Example IV fore the outside temperature reached 60 C. After the reaction mass had been cooled to so 0., TWO hundred Paris of a refined #40 White oil 413 parts of zinc dust was added and it was kept sulfonyl chloride obtained after the manner deat 60 C. for 3 hours and then cooled to 20 C. in R 2,202,791 a ple I) conand 222 parts of hydrochloric acid (concentratteimng alkane and chicroalkane primary and ed) was added. The temperature was raised to P and yonyl chlorides was the boil and kept there f 2 hours during which introduced into an autoclave with 1000 parts bentime 22.7 parts zinc dust was added in small 200 parts Mgo and 100 parts reduced amounts. The reaction mass was then stirred for 61 catalyst The charge was u d at 150 C. 12 hours and the .water-white upper oily layer under 700 of hydrogen for .5 ours after of a mixture of cetaneand chlorocetane-mer- 30 the last pressure drop- The Solids comprising captans was separated. Analysis: chlorine, catalyst e i e H analysis of the 7.35%; sulfur, 14.84%. Five parts of the homolobenzene Solution indicated SH, which corgous mixture of cetane mercaptan derivatives responds a Yield of 77% of White oil merwas dissolved in 50 parts warm alcohol and treatcaptaned with an alcoholic solution of mercuric chlo- In place of the mekel catalyst of a ple IV mm A white precipitate of the mercuric men may be substituted other hydrogenation catalysts captide formed at once. including Palledlum, Pletmiimcopper, copperchromite. Other acceptors such as calcium ox- Example II ide can be used in place of magnesium oxide.

- seventy parts zinc dust; 180 parts water and Still other useful acid acceptors include barium 200 parts of a homologous mixture of petrolatum sulfonyl chlorides, including primary, secf plaice of the high lmlecular weight 5111' ondary and chloro-sulfonyl chlorides, containony orides set forth m the abve examples mg 7.44% sulfur and 18.55% chlorine obtained f e substituted Other sulfenii chlflride by reacting petrolatum with admixed sulfur r vatives obtainable from saturated aliphatic hyoxide and chlorine after the manner set forth in ydmcarbons of at least 5 and Preferably at least U. S. Patent 2,202,791, were mixed and stirred 8 carbon atoms Including mixtures of S ch hytogether for 2 hours. There was then added 10 such as Petroleum bcn fracparts zinc dust and the reaction mass stirred for tions T the mixtures of 16 hours at room temperature, then 440 parts fonyl chloride derivatives obtainable from penconcentrated HCl was-added and the reaction tame octane nonanei decane, e Octemass refluxed 36 hours. light colored on decane, etc., refined kerosene, lubricating oils,

oxide, calcium hydroxide, and barium hydroxide.

containing petrolatum mercaptan derivatives inwhite paramn' scale e cluding chloro petrolatum mercaptans was septmatesmatch waxrAsietie .l ..and the satt i d hydrocarbon mixtures obtained by prac- Example I tlcing the processes described in British Patent 511,614 can be used as reactants. The petroleum Thirteen hundred and v parts water and hydrocarbon fractions may contain naphthene 525 parts zinc dust were mixed with 570 parts hydrocarbons 0f 3 0 8 Carbon atoms in various of a homologous mixture of cetane and chloro- Proportionscetane ulfonyl ghlorides including monoand Sulfonyl chloride derivatives free from chlopolysulfonyl primary and secondary derivatives Tine attached-t0 carbon as Well as those concontaining 8% sulfur and 24.2% chlorine obwining Such atoms are p ehended. Such tained after the manner described in Example I. derivatives are not t d t th e prepared The reaction masswarmed up to 70 C spontaby the process of Reed U. S. Reissue Patent 20,968.

neously. At this point 72 parts of zinc dust was on the contrary, Similar p ducts can be made added and t massstirred t 0 c for 2 hours from sulfuryl chloride and actinic light irradiaand then 3320 parts hydrochloric acid was gradtlon after the manner described in J. Am. Chem. ually added over a period of 2 hours. The tem- Soc. 61, (1939). Other processes of perature roseto the boil and 340 parts zinc dust making mixtures of P y a d se d ry sulwas added in small portions over the next 2 hours. fonyl chloride products free from chlorine at- The reaction mass was then heated at 100 C. tached to carbon are described in U. S. Patents for 36 hours. The zinc was not completely 2,146,7 47,346 and 2,142,934.

dissolved at this point and the liquid was de- Th inv nti n provides a smooth and ecocanted and the upper oily layer separated. This nomical route for the conversion of cheap paratasemce fin hydrocarbons to mixtures of mercaptans. These mercaptans may find use for the preparation of surface active chemicals or for conversion to metal mercaptides which are of value as in secticides, fungicides, bactericides and lubrieating oil addition agents.

As many apparently widely different embodiments of this invention may he made without de parting from the spirit and scope thereof it is to be understood that I do not limit myself to the specific embodiments thereof except as defined by the appended claims.

I claim.

1. The process which comprises reacting a mixture of saturated hydrocarbon sulionyl chlorides of at least 5 carbon atoms free from aromatic groups with a strong reducing agent and recov ering a mixture of mercaptans.

2. The process which comprises reacting a mixture of saturated aliphatic hydrocarbon sulionyi chlorides of at least 8 carbon atoms free from aromatic groups with a strong reducing agent at a temperature from 20 to 250 C. until a material amount of the sulionyl chloride has been converted to a mercaptan.

3. The process which comprises reacting a mixture of saturated aliphatic hydrocarbon primary and secondary sulfonyl chlorides of at least 8 carbon atoms free from aromatic groups with a strong reducing agent in a mineral acid media at a temperature .from 2o to 2563" C. until a material amount of the sulionyl. chloride has been converted to a mercaptan.

. The process which comprises reacting an isomeric mixture of primary and secondary 'alkane polysulfonyl chlorides and chloroalkane sulfonyl chlorides of at least 8 carbon atoms with a strong reducing agent at a temperature from 20 to 250 C. until a material amount of the sulfonyl chlorides have been converted to mercaptans.

5. The process which comprises reacting a homologous and isomeric mixture of primary and secondary alkane sulfonyl chlorides of at least eight carbon atoms in the hydrocarbon nuclei with a finely divided heavy metal in a dilute mineral acid solution at a temperature from 20 to 250 C. until a material amount of the sulfonyl chloride groups has been converted to mercaptan groups.

6. The process which comprises reacting a mixture of saturated hydrocarbon sulfonyl ch10 rides of at least 5 carbon atoms free from are-- matic groups with hydrogen in the presence of a hydrogenation catalyst.

'2. The process which comprises reacting a mixture of saturated hydrocarbon sulfonyl chlorides of at least 5 carbon atoms free from aromatic groups with hydrogen in the presence of a nickel catalyst.

8. iIhe process which comprises reacting a mixture of petroleum white 011 primary and seconolary sulionyl chlorides containing chlorine groups attached to carbon in a benzene solution with hydrogen in the presence of an acid ac ceptor and a reduced nickel catalyst. 

